Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807024270/lh2395sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807024270/lh2395Isup2.hkl |
CCDC reference: 650709
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.003 Å
- H-atom completeness 85%
- Disorder in main residue
- R factor = 0.023
- wR factor = 0.057
- Data-to-parameter ratio = 20.3
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT430_ALERT_2_B Short Inter D...A Contact O1W .. O2W .. 2.76 Ang.
Alert level C PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... ? PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O5 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Cl2 PLAT301_ALERT_3_C Main Residue Disorder ......................... 25.00 Perc. PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 50.00 Perc. PLAT430_ALERT_2_C Short Inter D...A Contact O2 .. O2W .. 2.85 Ang. PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 6 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2 O
Alert level G FORMU01_ALERT_2_G There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C20 H26 Ba1 Cl2 N6 O10 Atom count from the _atom_site data: C20 H22 Ba1 Cl2 N6 O10 CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected. CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional? From the CIF: _cell_formula_units_Z 4 From the CIF: _chemical_formula_sum C20 H26 Ba Cl2 N6 O10 TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 80.00 80.00 0.00 H 104.00 88.00 16.00 Ba 4.00 4.00 0.00 Cl 8.00 8.00 0.00 N 24.00 24.00 0.00 O 40.00 40.00 0.00 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 3
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 10 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
In 1990, the structure of a complex formulated as [Ba(C20H22N6)(ClO4)2(C2H5OH)], (II), was determined at ambient temperature and refined in space group Aa to a value of R = 0.080 for data with I > 2σ(I) (Harding et al., 1990). Low-temperature data for the title complex gave a unit cell apparently isomorphous with that of (II) and a similar solution in Cc, but the refinement was poor (see Supplementary Material). Solution in C2/c, however, gave a much better refinement for a model with disorder between one coordinated perchlorate anion and a coordinated water molecule across the twofold axis. While it is possible that both the title complex and (II) could differ in the coordinated solvent present and still have very similar unit cells, it is also possible that the complexes are the same and that the earlier structure should be re-interpreted.
Complex (I), [Ba(C20H22N6)(ClO4)2(H2O)]H2O, was prepared as reported previously (Harding et al., 1990) and recrystallized from CH3CN by slow diffusion of Et2O to yield colourless crystals.
H atoms bonded to C were inserted at calculated positions with C—H distances of 0.99 and 0.95 Å for saturated and unsaturated C atoms, respectively; they were refined using a riding model with Uiso(H) = 1.2Ueq(C). The H atoms bonded to partial occupancy O atoms were not located or included in the model.
The stucture of the title compound, [Ba(C20H22N6)(ClO4)2(H2O)].H2O, (I), was solved in C2/c and is shown in Fig. 1. The barium ion is 11-coordinate; it is bonded to all six N donors of the macrocycle, which is folded to accommodate the metal (N1—Ba—N1i , 130.69 (6)°). Two bidentate perchlorate anions are also coordinated, one on each side of the macrocycle, and the coordination sphere is completed by a water molecule (O1W) on the convex side. A non-coordinated water molecule (O2W) is H-bonded to O1W and to the perchlorate ion. A 2-fold axis runs through Ba1 and Cl1 and this requires that the perchlorate/water assembly on the convex face of the macrocycle is disordered with equal occupancy of two positions related by the 2-fold axis, as shown in Fig. 2. There is also a minor disorder in the saturated portion of the macrocycle at C9; this was modelled as 9:1 occupancy of two related sites.
The water molecules link the complex molecules into two-dimensional sheets perpendicular to a through further H-bonding (Table 1). The disorder of the groups coordinated on the convex face of the macrocycle gives rise to two possible H-bonding nets related by a 2-fold axis, one of these is shown in Fig. 3. The principal interaction between adjacent layers is π-π stacking of the pyridine-imine unit with the same section of an adjacent molecule under symmetry operation (iv) -x - 1/2, -y + 3/2, -z + 1 (Fig. 4). The mean interplanar distance between the overlapping sections (N1, N2, C1 – C6) is 3.441 Å. Interactions between layers are not affected significantly by the disorder within the two-dimensional H-bonded sheets, so the structure can be viewed as a random stack of the two H-bonded layers.
The structure was initially solved in Cc as the statistics indicated a non-centrosymmetric space group (possibly an artefact due to the presence of the heavy Ba atom). There was disorder evident on the convex side of the macrocycle, racemic twinning was indicated, the Flack parameter refined to 0.43 (2), and the anisotropic refinement required a series of restraints to prevent atoms going non-positive definite. Hence, the centrosymmetric solution was preferred.
In 1990, the structure of a complex formulated as [Ba(C20H22N6)(ClO4)2(C2H5OH)], (II), was determined at ambient temperature and refined in space group Aa to a value of R = 0.080 for data with I > 2σ(I) (Harding et al., 1990). Low-temperature data for the title complex gave a unit cell apparently isomorphous with that of (II) and a similar solution in Cc, but the refinement was poor (see Supplementary Material). Solution in C2/c, however, gave a much better refinement for a model with disorder between one coordinated perchlorate anion and a coordinated water molecule across the twofold axis. While it is possible that both the title complex and (II) could differ in the coordinated solvent present and still have very similar unit cells, it is also possible that the complexes are the same and that the earlier structure should be re-interpreted.
Data collection: APEX2 (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2001); software used to prepare material for publication: SHELXTL.
[Ba(ClO4)2(C20H22N6)(H2O)]·H2O | F(000) = 1432 |
Mr = 718.71 | Dx = 1.771 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 9994 reflections |
a = 14.5247 (8) Å | θ = 2.4–31.7° |
b = 12.0634 (6) Å | µ = 1.74 mm−1 |
c = 15.8698 (8) Å | T = 150 K |
β = 104.157 (1)° | Triangular prism, colourless |
V = 2696.2 (2) Å3 | 0.51 × 0.31 × 0.13 mm |
Z = 4 |
Bruker APEXII diffractometer | 4334 independent reflections |
Radiation source: fine-focus sealed tube | 4120 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
φ and ω scans | θmax = 31.9°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −21→21 |
Tmin = 0.472, Tmax = 0.806 | k = −17→17 |
16000 measured reflections | l = −23→23 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.023 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.057 | H-atom parameters constrained |
S = 1.19 | w = 1/[σ2(Fo2) + (0.0204P)2 + 4.1932P] where P = (Fo2 + 2Fc2)/3 |
4334 reflections | (Δ/σ)max = 0.002 |
213 parameters | Δρmax = 0.69 e Å−3 |
3 restraints | Δρmin = −0.63 e Å−3 |
[Ba(ClO4)2(C20H22N6)(H2O)]·H2O | V = 2696.2 (2) Å3 |
Mr = 718.71 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 14.5247 (8) Å | µ = 1.74 mm−1 |
b = 12.0634 (6) Å | T = 150 K |
c = 15.8698 (8) Å | 0.51 × 0.31 × 0.13 mm |
β = 104.157 (1)° |
Bruker APEXII diffractometer | 4334 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 4120 reflections with I > 2σ(I) |
Tmin = 0.472, Tmax = 0.806 | Rint = 0.018 |
16000 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | 3 restraints |
wR(F2) = 0.057 | H-atom parameters constrained |
S = 1.19 | Δρmax = 0.69 e Å−3 |
4334 reflections | Δρmin = −0.63 e Å−3 |
213 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ba1 | 0.0000 | 0.788958 (11) | 0.7500 | 0.01874 (4) | |
N1 | −0.10892 (11) | 0.68917 (13) | 0.59159 (10) | 0.0238 (3) | |
C1 | −0.06707 (14) | 0.65105 (15) | 0.53091 (12) | 0.0256 (3) | |
C2 | −0.11248 (16) | 0.57923 (18) | 0.46426 (13) | 0.0338 (4) | |
H2 | −0.0805 | 0.5533 | 0.4225 | 0.041* | |
C3 | −0.20456 (17) | 0.54690 (18) | 0.46044 (15) | 0.0381 (5) | |
H3 | −0.2369 | 0.4977 | 0.4163 | 0.046* | |
C4 | −0.24903 (15) | 0.58707 (17) | 0.52181 (15) | 0.0352 (4) | |
H4 | −0.3127 | 0.5669 | 0.5200 | 0.042* | |
C5 | −0.19879 (13) | 0.65772 (15) | 0.58645 (13) | 0.0267 (4) | |
C6 | −0.24753 (13) | 0.70665 (17) | 0.64921 (14) | 0.0302 (4) | |
H6 | −0.3125 | 0.6892 | 0.6436 | 0.036* | |
N2 | −0.20673 (11) | 0.77051 (14) | 0.70992 (11) | 0.0266 (3) | |
C7 | −0.26778 (15) | 0.8175 (2) | 0.76233 (14) | 0.0356 (4) | 0.90 |
H7A | −0.3350 | 0.8113 | 0.7297 | 0.043* | 0.90 |
H7B | −0.2529 | 0.8972 | 0.7726 | 0.043* | 0.90 |
C8 | −0.25451 (17) | 0.7586 (2) | 0.84939 (17) | 0.0383 (5) | 0.90 |
H8A | −0.3117 | 0.7722 | 0.8714 | 0.046* | 0.90 |
H8B | −0.2511 | 0.6779 | 0.8394 | 0.046* | 0.90 |
C9 | −0.16824 (16) | 0.7917 (2) | 0.91937 (15) | 0.0407 (5) | 0.90 |
H9A | −0.1659 | 0.8736 | 0.9230 | 0.049* | 0.90 |
H9B | −0.1760 | 0.7636 | 0.9758 | 0.049* | 0.90 |
C7' | −0.26778 (15) | 0.8175 (2) | 0.76233 (14) | 0.0356 (4) | 0.10 |
H7'1 | −0.3091 | 0.7577 | 0.7752 | 0.043* | 0.10 |
H7'2 | −0.3095 | 0.8740 | 0.7270 | 0.043* | 0.10 |
C8' | −0.2141 (14) | 0.8725 (14) | 0.8508 (9) | 0.032 (4)* | 0.10 |
H8'1 | −0.1647 | 0.9230 | 0.8396 | 0.038* | 0.10 |
H8'2 | −0.2598 | 0.9178 | 0.8730 | 0.038* | 0.10 |
C9' | −0.16824 (16) | 0.7917 (2) | 0.91937 (15) | 0.0407 (5) | 0.10 |
H9'1 | −0.1576 | 0.8276 | 0.9770 | 0.049* | 0.10 |
H9'2 | −0.2113 | 0.7279 | 0.9185 | 0.049* | 0.10 |
N3 | −0.07714 (12) | 0.75158 (15) | 0.90665 (11) | 0.0275 (3) | |
C10 | −0.02915 (14) | 0.69174 (16) | 0.96740 (12) | 0.0280 (4) | |
H10 | −0.0564 | 0.6722 | 1.0140 | 0.034* | |
Cl1 | 0.0000 | 0.48758 (5) | 0.7500 | 0.02468 (12) | |
O1 | −0.07104 (10) | 0.55775 (11) | 0.77253 (10) | 0.0303 (3) | |
O2 | −0.04305 (13) | 0.41910 (14) | 0.67689 (12) | 0.0444 (4) | |
Cl2 | −0.00155 (6) | 1.03329 (8) | 0.62396 (6) | 0.02486 (16) | 0.50 |
O5 | −0.0806 (3) | 0.9790 (3) | 0.6470 (2) | 0.0381 (8) | 0.50 |
O6 | −0.0092 (3) | 1.1495 (3) | 0.6331 (2) | 0.0408 (7) | 0.50 |
O7 | 0.0840 (2) | 0.9913 (3) | 0.6816 (2) | 0.0342 (6) | 0.50 |
O8 | −0.0029 (4) | 1.0072 (4) | 0.5355 (2) | 0.0576 (11) | 0.50 |
O1W | 0.0299 (4) | 0.9723 (3) | 0.8653 (2) | 0.0476 (10) | 0.50 |
O2W | −0.0057 (4) | 1.1901 (4) | 0.8142 (3) | 0.0690 (13) | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ba1 | 0.02017 (7) | 0.01853 (7) | 0.01998 (7) | 0.000 | 0.00965 (5) | 0.000 |
N1 | 0.0224 (7) | 0.0224 (7) | 0.0265 (7) | 0.0014 (5) | 0.0054 (5) | −0.0012 (5) |
C1 | 0.0281 (8) | 0.0230 (8) | 0.0245 (8) | 0.0044 (7) | 0.0042 (7) | −0.0026 (6) |
C2 | 0.0399 (11) | 0.0295 (9) | 0.0289 (9) | 0.0056 (8) | 0.0024 (8) | −0.0071 (7) |
C3 | 0.0404 (11) | 0.0286 (10) | 0.0378 (11) | −0.0005 (8) | −0.0049 (9) | −0.0072 (8) |
C4 | 0.0270 (9) | 0.0284 (9) | 0.0449 (12) | −0.0020 (8) | −0.0014 (8) | −0.0016 (8) |
C5 | 0.0219 (8) | 0.0226 (8) | 0.0338 (9) | 0.0016 (6) | 0.0035 (7) | 0.0016 (7) |
C6 | 0.0186 (8) | 0.0313 (9) | 0.0411 (11) | 0.0017 (7) | 0.0083 (7) | 0.0053 (8) |
N2 | 0.0225 (7) | 0.0299 (8) | 0.0301 (8) | 0.0078 (6) | 0.0115 (6) | 0.0064 (6) |
C7 | 0.0272 (9) | 0.0482 (12) | 0.0351 (10) | 0.0139 (9) | 0.0151 (8) | 0.0067 (9) |
C8 | 0.0255 (10) | 0.0550 (15) | 0.0400 (12) | 0.0071 (10) | 0.0189 (9) | 0.0136 (11) |
C9 | 0.0325 (10) | 0.0636 (15) | 0.0322 (10) | 0.0116 (10) | 0.0201 (8) | 0.0035 (10) |
C7' | 0.0272 (9) | 0.0482 (12) | 0.0351 (10) | 0.0139 (9) | 0.0151 (8) | 0.0067 (9) |
C9' | 0.0325 (10) | 0.0636 (15) | 0.0322 (10) | 0.0116 (10) | 0.0201 (8) | 0.0035 (10) |
N3 | 0.0253 (7) | 0.0348 (8) | 0.0258 (7) | 0.0016 (6) | 0.0131 (6) | 0.0015 (6) |
C10 | 0.0307 (9) | 0.0322 (9) | 0.0235 (8) | −0.0059 (7) | 0.0115 (7) | 0.0018 (7) |
Cl1 | 0.0260 (3) | 0.0175 (2) | 0.0348 (3) | 0.000 | 0.0156 (2) | 0.000 |
O1 | 0.0296 (7) | 0.0251 (6) | 0.0411 (8) | 0.0065 (5) | 0.0178 (6) | 0.0012 (6) |
O2 | 0.0469 (9) | 0.0358 (8) | 0.0572 (10) | −0.0167 (7) | 0.0258 (8) | −0.0204 (8) |
Cl2 | 0.0288 (4) | 0.0247 (4) | 0.0219 (4) | −0.0025 (3) | 0.0077 (3) | 0.0058 (3) |
O5 | 0.0302 (16) | 0.0428 (19) | 0.0391 (18) | −0.0088 (14) | 0.0041 (14) | 0.0120 (14) |
O6 | 0.059 (2) | 0.0259 (15) | 0.0359 (17) | 0.0034 (14) | 0.0078 (15) | 0.0003 (13) |
O7 | 0.0227 (13) | 0.0346 (15) | 0.0444 (17) | 0.0007 (11) | 0.0065 (12) | 0.0083 (13) |
O8 | 0.095 (3) | 0.055 (2) | 0.0287 (16) | 0.011 (2) | 0.0268 (19) | 0.0088 (15) |
O1W | 0.091 (3) | 0.0312 (18) | 0.0255 (16) | −0.004 (2) | 0.022 (2) | −0.0022 (13) |
O2W | 0.093 (4) | 0.050 (2) | 0.065 (3) | 0.002 (2) | 0.022 (3) | −0.003 (2) |
Ba1—O1W | 2.836 (4) | N2—C7 | 1.470 (2) |
Ba1—N1 | 2.8856 (16) | C7—C8 | 1.523 (3) |
Ba1—O5 | 2.893 (4) | C7—H7A | 0.9900 |
Ba1—N2 | 2.9217 (16) | C7—H7B | 0.9900 |
Ba1—N3 | 3.0002 (15) | C8—C9 | 1.511 (4) |
Ba1—O1 | 3.0253 (14) | C8—H8A | 0.9900 |
Ba1—O7 | 3.045 (3) | C8—H8B | 0.9900 |
N1—C1 | 1.340 (2) | C9—N3 | 1.469 (3) |
N1—C5 | 1.342 (2) | C9—H9A | 0.9900 |
C1—C2 | 1.401 (3) | C9—H9B | 0.9900 |
C1—C10i | 1.475 (3) | C8'—H8'1 | 0.9900 |
C2—C3 | 1.380 (3) | C8'—H8'2 | 0.9900 |
C2—H2 | 0.9500 | N3—C10 | 1.268 (3) |
C3—C4 | 1.381 (3) | C10—H10 | 0.9500 |
C3—H3 | 0.9500 | Cl1—O2 | 1.4369 (17) |
C4—C5 | 1.395 (3) | Cl1—O1 | 1.4455 (13) |
C4—H4 | 0.9500 | Cl2—O6 | 1.416 (3) |
C5—C6 | 1.479 (3) | Cl2—O8 | 1.435 (3) |
C6—N2 | 1.262 (3) | Cl2—O7 | 1.442 (3) |
C6—H6 | 0.9500 | Cl2—O5 | 1.444 (3) |
O1W—Ba1—N1 | 148.48 (11) | N1—C1—C2 | 122.83 (19) |
O1W—Ba1—N1i | 78.38 (9) | N1—C1—C10i | 117.85 (16) |
N1—Ba1—N1i | 130.69 (6) | C2—C1—C10i | 119.24 (18) |
O1W—Ba1—O5i | 16.22 (10) | C3—C2—C1 | 118.7 (2) |
N1—Ba1—O5i | 152.02 (8) | C3—C2—H2 | 120.7 |
O1W—Ba1—O5 | 73.93 (10) | C1—C2—H2 | 120.7 |
N1—Ba1—O5 | 77.19 (8) | C2—C3—C4 | 119.02 (19) |
N1i—Ba1—O5 | 152.02 (8) | C2—C3—H3 | 120.5 |
O5i—Ba1—O5 | 75.11 (15) | C4—C3—H3 | 120.5 |
O1W—Ba1—N2 | 100.79 (12) | C3—C4—C5 | 118.8 (2) |
N1—Ba1—N2 | 57.54 (5) | C3—C4—H4 | 120.6 |
N1i—Ba1—N2 | 118.24 (4) | C5—C4—H4 | 120.6 |
O5i—Ba1—N2 | 115.84 (8) | N1—C5—C4 | 122.92 (19) |
O5—Ba1—N2 | 71.63 (8) | N1—C5—C6 | 117.70 (17) |
O1W—Ba1—N2i | 86.08 (12) | C4—C5—C6 | 119.26 (18) |
N1—Ba1—N2i | 118.24 (4) | N2—C6—C5 | 123.03 (17) |
O5—Ba1—N2i | 115.84 (8) | N2—C6—H6 | 118.5 |
N2—Ba1—N2i | 171.27 (6) | C5—C6—H6 | 118.5 |
O1W—Ba1—N3 | 67.18 (9) | C6—N2—C7 | 115.58 (18) |
N1—Ba1—N3 | 115.02 (5) | C6—N2—Ba1 | 118.57 (12) |
N1i—Ba1—N3 | 56.75 (4) | C7—N2—Ba1 | 125.28 (13) |
O5i—Ba1—N3 | 80.34 (9) | N2—C7—C8 | 111.95 (18) |
O5—Ba1—N3 | 113.95 (9) | N2—C7—H7A | 109.2 |
N2—Ba1—N3 | 66.22 (5) | C8—C7—H7A | 109.2 |
N2i—Ba1—N3 | 112.35 (5) | N2—C7—H7B | 109.2 |
O1W—Ba1—N3i | 128.49 (9) | C8—C7—H7B | 109.2 |
N1—Ba1—N3i | 56.75 (4) | H7A—C7—H7B | 107.9 |
O5—Ba1—N3i | 80.34 (9) | C9—C8—C7 | 116.2 (2) |
N2—Ba1—N3i | 112.35 (5) | C9—C8—H8A | 108.2 |
N3—Ba1—N3i | 162.71 (7) | C7—C8—H8A | 108.2 |
O1W—Ba1—O1 | 130.24 (8) | C9—C8—H8B | 108.2 |
N1—Ba1—O1 | 65.68 (4) | C7—C8—H8B | 108.2 |
N1i—Ba1—O1 | 69.06 (4) | H8A—C8—H8B | 107.4 |
O5i—Ba1—O1 | 140.06 (9) | N3—C9—C8 | 115.15 (19) |
O5—Ba1—O1 | 134.03 (7) | N3—C9—H9A | 108.5 |
N2—Ba1—O1 | 66.01 (4) | C8—C9—H9A | 108.5 |
N2i—Ba1—O1 | 105.43 (4) | N3—C9—H9B | 108.5 |
N3—Ba1—O1 | 63.66 (4) | C8—C9—H9B | 108.5 |
N3i—Ba1—O1 | 99.59 (4) | H9A—C9—H9B | 107.5 |
O1W—Ba1—O1i | 142.43 (10) | H8'1—C8'—H8'2 | 107.6 |
N1—Ba1—O1i | 69.06 (4) | C10—N3—C9 | 115.43 (17) |
O5—Ba1—O1i | 140.06 (9) | C10—N3—Ba1 | 117.93 (12) |
N2—Ba1—O1i | 105.43 (4) | C9—N3—Ba1 | 126.58 (13) |
N3—Ba1—O1i | 99.59 (4) | N3—C10—C1i | 123.05 (17) |
O1—Ba1—O1i | 45.57 (5) | N3—C10—H10 | 118.5 |
O1W—Ba1—O7i | 32.46 (13) | C1i—C10—H10 | 118.5 |
O1W—Ba1—O7 | 65.97 (10) | O2—Cl1—O2i | 109.81 (16) |
N1—Ba1—O7i | 117.57 (6) | O2—Cl1—O1 | 109.90 (10) |
N1—Ba1—O7 | 101.89 (7) | O2i—Cl1—O1 | 109.45 (9) |
O5—Ba1—O7 | 45.97 (9) | O1i—Cl1—O1 | 108.31 (12) |
O5—Ba1—O7i | 54.82 (11) | Cl1—O1—Ba1 | 103.06 (7) |
N2—Ba1—O7i | 70.05 (6) | O6—Cl2—O8 | 109.6 (2) |
N2—Ba1—O7 | 117.60 (6) | O6—Cl2—O7 | 111.0 (2) |
N3—Ba1—O7i | 64.02 (7) | O8—Cl2—O7 | 110.3 (2) |
N3—Ba1—O7 | 132.77 (7) | O6—Cl2—O5 | 109.6 (2) |
O1—Ba1—O7i | 121.28 (6) | O8—Cl2—O5 | 109.1 (3) |
O1—Ba1—O7 | 163.58 (7) | O7—Cl2—O5 | 107.18 (19) |
C1—N1—C5 | 117.70 (16) | Cl2—O5—Ba1 | 105.37 (18) |
C1—N1—Ba1 | 121.39 (12) | Cl2—O7—Ba1 | 98.60 (14) |
C5—N1—Ba1 | 119.25 (12) |
Symmetry code: (i) −x, y, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Ba(ClO4)2(C20H22N6)(H2O)]·H2O |
Mr | 718.71 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 150 |
a, b, c (Å) | 14.5247 (8), 12.0634 (6), 15.8698 (8) |
β (°) | 104.157 (1) |
V (Å3) | 2696.2 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.74 |
Crystal size (mm) | 0.51 × 0.31 × 0.13 |
Data collection | |
Diffractometer | Bruker APEXII |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.472, 0.806 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16000, 4334, 4120 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.744 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.057, 1.19 |
No. of reflections | 4334 |
No. of parameters | 213 |
No. of restraints | 3 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.69, −0.63 |
Computer programs: APEX2 (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 2001), SHELXTL.
D···A | D···A | D···A | D···A |
O1W···O2W | 2.761 (6) | O2W···O6 | 2.904 (7) |
O1W···O8i | 2.866 (5) | O2W···O2ii | 2.846 (5) |
Symmetry codes: (i) x, -y+2, z+1/2; (ii) -x, y+1, -z+3/2. |
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The stucture of the title compound, [Ba(C20H22N6)(ClO4)2(H2O)].H2O, (I), was solved in C2/c and is shown in Fig. 1. The barium ion is 11-coordinate; it is bonded to all six N donors of the macrocycle, which is folded to accommodate the metal (N1—Ba—N1i , 130.69 (6)°). Two bidentate perchlorate anions are also coordinated, one on each side of the macrocycle, and the coordination sphere is completed by a water molecule (O1W) on the convex side. A non-coordinated water molecule (O2W) is H-bonded to O1W and to the perchlorate ion. A 2-fold axis runs through Ba1 and Cl1 and this requires that the perchlorate/water assembly on the convex face of the macrocycle is disordered with equal occupancy of two positions related by the 2-fold axis, as shown in Fig. 2. There is also a minor disorder in the saturated portion of the macrocycle at C9; this was modelled as 9:1 occupancy of two related sites.
The water molecules link the complex molecules into two-dimensional sheets perpendicular to a through further H-bonding (Table 1). The disorder of the groups coordinated on the convex face of the macrocycle gives rise to two possible H-bonding nets related by a 2-fold axis, one of these is shown in Fig. 3. The principal interaction between adjacent layers is π-π stacking of the pyridine-imine unit with the same section of an adjacent molecule under symmetry operation (iv) -x - 1/2, -y + 3/2, -z + 1 (Fig. 4). The mean interplanar distance between the overlapping sections (N1, N2, C1 – C6) is 3.441 Å. Interactions between layers are not affected significantly by the disorder within the two-dimensional H-bonded sheets, so the structure can be viewed as a random stack of the two H-bonded layers.
The structure was initially solved in Cc as the statistics indicated a non-centrosymmetric space group (possibly an artefact due to the presence of the heavy Ba atom). There was disorder evident on the convex side of the macrocycle, racemic twinning was indicated, the Flack parameter refined to 0.43 (2), and the anisotropic refinement required a series of restraints to prevent atoms going non-positive definite. Hence, the centrosymmetric solution was preferred.